CN102515618A - Slow release slump retaining polycarboxylate water reducer and preparation thereof - Google Patents
Slow release slump retaining polycarboxylate water reducer and preparation thereof Download PDFInfo
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Abstract
The invention relates to a slow release slump retaining polycarboxylate water reducer and a preparation method thereof. The method comprises the specific steps of: carrying out ration on unsaturated polyoxyethylene ether, acrylic acid, acrylic acid ester monomers, crosslinking monomer, initiator, chain transferring agent and water for 4-7 h at a reaction temperature of 80-90 DEG C; cooling to 35-40 DEG C; adjusting a pH value of the solution to neutral to obtain a colorless and transparent solution, namely the slow release slump retaining polycarboxylate water reducer. The water reducer prepared by the invention employs two modes of hydrolysis and maintains functions in a cement system for a long time through hydrolysis of ester group on polyacrylic acid monomers and ester group on crosslinking monomer, so as to realize control of slump loss. The slow release slump retaining polycarboxylate water reducer can obviously increase net paste fluidity after one hour, has good retentivity on net paste fluidity after two hours and can maintain nearly zero loss on slump after one hour.
Description
Technical field
The present invention relates to a kind of slowly-releasing collapse protective poly-carboxylic acid water reducing agent and preparation method thereof.
Background technology
Present concrete just develops towards the direction of high performance and multifunction, requires concrete to have high workability, HS, high-durability, and can satisfy in many application in particular cases.
For ready mixed concrete industry, when concrete mix must transport for a long time, should keep initial slump level as much as possible.The excessive method of solution concrete slump loss relatively more commonly used is with water reducer and the compound use of retardant; Through the retarding action of retardant to hydrated cementitious; The hydration rate of cement can slow down; Keep the lubricated solid particulate of more moisture, reach the purpose that cement slurry and concrete flowability loss are newly mixed in minimizing.In order to prepare efficiently, have the collapse water reducer of effect of long-time guarantor, many researchists have done a large amount of research and exploration.
Patent CN101205127A has introduced a kind of prescription and method of manufacture thereof of sustained release type polycarboxylic acid series high-performance dehydragent.Prescription comprises esterification prescription and polymerization reaction formulation, and the esterification prescription adopts a part of MALEIC ANHYDRIDE, and molecular weight is 600 poly glycol monomethyl ether, hydroquinone of polymerization retarder, and the catalyzer tosic acid and the vitriol oil are raw material.Add MALEIC ANHYDRIDE down earlier at 75 ℃, molecular weight is 600 poly glycol monomethyl ether, hydroquinone of polymerization retarder, and catalyzer tosic acid reaction 2 hours adds the vitriol oil again and continues isothermal reaction 3 hours.Polymerization process is that the MALEIC ANHYDRIDE of remainder, allyl polyethenoxy ether (polymerization degree is 26), water are joined in the reaction kettle of the esterification of front; Vinylformic acid, methylpropene sodium sulfonate are added the water wiring solution-forming, and ammonium persulphate adds the water wiring solution-forming, is added drop-wise to respectively in the reaction kettle; The dropping time is 2 hours; Isothermal reaction 1.5 hours cools to 50 ℃ and adds the liquid caustic soda neutralization, obtains sustained release type polycarboxylic acid series high-performance dehydragent.It is very fast that this invention adopts maleic anhydride to do its hydrolysis rate of reaction monomers, and slow release speed and performance still are not very desirable.
Patent CN102040741A has introduced a kind of method for preparing sustained-release polycarboxylic water reducer with the group of molecules packing technique.Its process step was divided into for two steps, and the first step is a polyreaction, and its composition of raw materials is big monomer, minor comonomer, Thiovanic acid and ammonium persulphate, and raw material is made into the aqueous solution, under 50 ~ 100 ℃, above-mentioned drips of solution was added in the water, continued reaction and obtained assembling precursor; Second step will be assembled precursor under 50 ~ 70 ℃, add the assembling agent, stir to add sodium hydroxide, obtain sustained-release polycarboxylic water reducer.This water reducer is to the fluctuation of concrete raw material quality, has very excellent flexibility, but this water reducer when in concrete, using the water reducer volume higher.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of slowly-releasing collapse protective poly-carboxylic acid water reducing agent; Prepared water reducer is in the cement alkaline environment; Two kinds of hydrolysis pattern through the water reducer molecule have effectively suppressed concrete slump loss, can keep preferable performance in a long time.
In order to achieve the above object, the present invention adopts following technical scheme:
A kind of slowly-releasing collapse protective poly-carboxylic acid water reducing agent is characterized in that the structural formula of this water reducer is:
（1）
R wherein
1, R
2, R
3, R
5, R
6, R
7, R
9And R
10Be respectively H or methyl; X is the molecule fragment after cross-linking monomer carries out crosslinking reaction; R
4And R
8Be respectively at least a in methyl, ethyl, hydroxyethyl, the hydroxypropyl; n
1~ n
7Be integer, wherein n
1And n
4Be 750～1500, n
2And n
6Be 25～55, n
3And n
5Be 250～500;
（2）
R wherein
1, R
2And R
4Be respectively H or methyl; R
3At least a in methyl, ethyl, hydroxyethyl, the hydroxypropyl; n
1~ n
7Be integer, wherein n
1Be 750～1500, n
2Be 25～55, n
3Be 250～500.
A kind of method for preparing above-mentioned slowly-releasing collapse protective poly-carboxylic acid water reducing agent is characterized in that the concrete steps of this method are following:
The composition and the mass percent of the raw material that a. adopts are:
The big monomer 32 ~ 39% of unsaturated polyoxy Vinyl Ether
Vinylformic acid 2.4 ~ 3.3%
Acrylic ester monomer 0.8 ~ 1.6%
Cross-linking monomer 0 ~ 0.5%
Chain-transfer agent 0.08 ~ 0.19%
Initiator 0.16 ~ 0.33%
The deionized water surplus;
B. with above-mentioned raw materials under 80～90 ℃ of temperature, the reaction times is 1～4 hour, is cooled to 35 ℃～40 ℃ then, regulator solution pH value obtains water white solution to neutral, is the slowly-releasing collapse protective poly-carboxylic acid water reducing agent.
The above-mentioned big monomer of unsaturated polyoxy Vinyl Ether can be allyl polyglycol ether or methacrylic polyglycol ether, and molecular weight is between 1000～2400.
Above-mentioned acrylic ester monomer can be in methyl acrylate, TEB 3K, ethyl propenoate, Hydroxyethyl acrylate, the Propylene glycol monoacrylate at least a.
Above-mentioned cross-linking monomer can be in glycol methacrylate, triethylene Glycol double methyl methacrylate, the multicondensed ethylene glycol double methyl methacrylate at least a.
Above-mentioned initiator can be ammonium persulphate, Potassium Persulphate or Sodium Persulfate.
Above-mentioned chain-transfer agent can be in mercaptoethanol, Thiovanic acid, 2-Thiovanic acid, 3-Thiovanic acid, thiohydracrylic acid, methylpropene sodium sulfonate and the sodium allyl sulfonate at least a.
Above-mentioned pH regulator agent can be the aqueous solution of quadrol, trolamine, Pottasium Hydroxide or sodium hydroxide.
The slowly-releasing collapse protective poly-carboxylic acid water reducing agent of the present invention's preparation has adopted two kinds of hydrolysis pattern.Owing to contain a large amount of ester groups in the water reducer molecular structure, can slowly hydrolysis in the alkaline environment that hydrated cementitious provides, discharge carboxylic acid ion, add in the cement system, produce the function of slump protection that continues.In addition, also introduce the slower cross-linking monomer of hydrolysis rate, behind water reducer intramolecularly hydrolysis of ester group, can also discharge a small amount of carboxylic acid ion like this; What is more important can make the structure of water reducer molecular gel shape progressively open, and launches its molecular chain at leisure; Discharge the carboxyl and the polyoxy alkyl group side chain that are wrapped in the gel structure; Further improve the water reducer performance, thereby produce more persistent function of slump protection, solved the too fast difficult problem of slump-loss in the engineering.
Embodiment
To help to understand the present invention through following examples, but not limit content of the present invention.
Embodiment one:50g methacrylic polyglycol ether, 3.75g vinylformic acid, 1.79g methyl acrylate, 0.15g glycol methacrylate, 0.39g ammonium persulphate, 0.20g thiohydracrylic acid, 83.30g deionized water are joined in the four-hole bottle; Heating in water bath to 85 ℃; Reacted 3 hours; Be cooled to 40 ℃, using mass concentration is that 20% sodium hydroxide is regulated pH value to neutrality, obtains solid content and be 40% slowly-releasing collapse protective poly-carboxylic acid water reducing agent.
Embodiment two:50g methacrylic polyglycol ether and 33.30g deionized water are joined in the four-hole bottle heating in water bath.3.75g vinylformic acid, 0.15g triethylene Glycol double methyl methacrylate and 1.79g methyl acrylate are mixed, 0.39g ammonium persulphate and 0.20g thiohydracrylic acid are added 50g deionized water wiring solution-forming.When treating that temperature is heated to 85 ℃, drip above-mentioned two kinds of mixed solutions respectively, the dropping time is 3 hours; Dropwised the back insulation reaction 2 hours; Be cooled to 40 ℃, using mass concentration is that 20% sodium hydroxide is regulated pH value to neutrality, obtains solid content and be 40% slowly-releasing collapse protective poly-carboxylic acid water reducing agent.
Embodiment three:50g methacrylic polyglycol ether, 3.75g vinylformic acid, 2.08g ethyl propenoate, 0.15g glycol methacrylate, 0.39g ammonium persulphate, 0.20g thiohydracrylic acid, 83.70g deionized water are joined in the four-hole bottle; Heating in water bath to 85 ℃; Reacted 3 hours; Be cooled to 40 ℃, using mass concentration is that 20% sodium hydroxide is regulated pH value to neutrality, obtains solid content and be 40% slowly-releasing collapse protective poly-carboxylic acid water reducing agent.
Embodiment four:50g methacrylic polyglycol ether and 33.70g deionized water are joined in the four-hole bottle heating in water bath.3.75g vinylformic acid, 0.15g glycol methacrylate and 2.08g ethyl propenoate are mixed, obtain monomer mixed solution; 0.39g ammonium persulphate and 0.20g thiohydracrylic acid are added 50g water wiring solution-forming.When treating that temperature is heated to 85 ℃, drip above-mentioned two kinds of mixed solutions respectively, the dropping time is 3 hours; Dropwised the back insulation reaction 2 hours; Be cooled to 40 ℃, using mass concentration is that 20% sodium hydroxide is regulated pH value to neutrality, obtains solid content and be 40% slowly-releasing collapse protective poly-carboxylic acid water reducing agent.
Embodiment five:50g methacrylic polyglycol ether, 3.75g vinylformic acid, 2.42g Hydroxyethyl acrylate, 0.15g glycol methacrylate, 0.39g ammonium persulphate, 0.20g thiohydracrylic acid, 84.20g deionized water are joined in the four-hole bottle; Heating in water bath to 85 ℃; Reacted 3 hours; Be cooled to 40 ℃, using mass concentration is that 20% sodium hydroxide is regulated pH value to neutrality, obtains solid content and be 40% slowly-releasing collapse protective poly-carboxylic acid water reducing agent.
Embodiment six:50g methacrylic polyglycol ether and 34.20g deionized water are joined in the four-hole bottle heating in water bath.3.75g vinylformic acid, 0.15g glycol methacrylate and 2.42g Hydroxyethyl acrylate are mixed, obtain monomer mixed solution; 0.39g ammonium persulphate and 0.20g thiohydracrylic acid are added 50g water wiring solution-forming.When treating that temperature is heated to 85 ℃, drip above-mentioned two kinds of mixed solutions respectively, the dropping time is 3 hours; Dropwised the back insulation reaction 2 hours; Be cooled to 40 ℃, using mass concentration is that 20% sodium hydroxide is regulated pH value to neutrality, obtains solid content and be 40% slowly-releasing collapse protective poly-carboxylic acid water reducing agent.
Embodiment seven:50g methacrylic polyglycol ether and 33.80g deionized water are joined in the four-hole bottle heating in water bath.3.75g vinylformic acid, 0.20g glycol methacrylate, 1.12g Hydroxyethyl acrylate and 1.04g ethyl propenoate are mixed, obtain monomer mixed solution; 0.39g ammonium persulphate and 0.20g thiohydracrylic acid are added 50g water wiring solution-forming.When treating that temperature is heated to 85 ℃, drip above-mentioned two kinds of mixed solutions respectively, the dropping time is 3 hours; Dropwised the back insulation reaction 2 hours; Be cooled to 40 ℃, using mass concentration is that 20% sodium hydroxide is regulated pH value to neutrality, obtains solid content and be 40% slowly-releasing collapse protective poly-carboxylic acid water reducing agent.
Embodiment eight:50g methacrylic polyglycol ether and 33.60g deionized water are joined in the four-hole bottle heating in water bath.3.75g vinylformic acid, 0.25g triethylene Glycol double methyl methacrylate, 1.12g Hydroxyethyl acrylate and 0.89g methyl acrylate are mixed, obtain monomer mixed solution; 0.39g ammonium persulphate and 0.20g thiohydracrylic acid are added 50g water wiring solution-forming.When treating that temperature is heated to 85 ℃, drip above-mentioned two kinds of mixed solutions respectively, the dropping time is 3 hours; Dropwised the back insulation reaction 2 hours; Be cooled to 40 ℃, using mass concentration is that 20% sodium hydroxide is regulated pH value to neutrality, obtains solid content and be 40% slowly-releasing collapse protective poly-carboxylic acid water reducing agent.
Embodiment nine:50g methacrylic polyglycol ether and 33.50g deionized water are joined in the four-hole bottle heating in water bath.3.75g vinylformic acid, 0.89g methyl acrylate, 0.10g glycol methacrylate, 0.15g triethylene Glycol double methyl methacrylate and 1.04g ethyl propenoate are mixed, obtain monomer mixed solution; 0.39g ammonium persulphate and 0.20g thiohydracrylic acid are added 50g water wiring solution-forming.When treating that temperature is heated to 85 ℃, drip above-mentioned two kinds of mixed solutions respectively, the dropping time is 3 hours; Dropwised the back insulation reaction 2 hours; Be cooled to 40 ℃, using mass concentration is that 20% sodium hydroxide is regulated pH value to neutrality, obtains solid content and be 40% slowly-releasing collapse protective poly-carboxylic acid water reducing agent.
Experiment effect
Test determination the clean slurry degree of mobilization and the concrete test data of sample under the identical volume.Test is carried out according to GB/T8077-2000 " Methods for testing uniformity of concrete admixture "; W/C=0.29; Volume is the solid volume of folding; The volume of slowly-releasing collapse protective poly-carboxylic acid water reducing agent is 0.16% of a cement quality during flowing degree of net paste of cement test, and the volume of slowly-releasing collapse protective poly-carboxylic acid water reducing agent is 0.2% of a cement quality during concrete test, and test-results is seen table 1 and table 2.
Table 1The flowing degree of net paste of cement data
Table2 is embodiment concrete data.
Claims (8)
1. slowly-releasing collapse protective poly-carboxylic acid water reducing agent is characterized in that the structural formula of this water reducer is:
（1）
R wherein
1, R
2, R
3, R
5, R
6, R
7, R
9And R
10Be respectively H or methyl; X is the molecule fragment after cross-linking monomer carries out crosslinking reaction; R
4And R
8Be respectively at least a in methyl, ethyl, hydroxyethyl, the hydroxypropyl; n
1~ n
7Be integer, wherein n
1And n
4Be 750～1500, n
2And n
6Be 25～55, n
3And n
5Be 250～500;
（2）
R wherein
1, R
2And R
4Be respectively H or methyl; R
3At least a in methyl, ethyl, hydroxyethyl, the hydroxypropyl; n
1~ n
7Be integer, wherein n
1Be 750～1500, n
2Be 25～55, n
3Be 250～500.
2. method for preparing slowly-releasing collapse protective poly-carboxylic acid water reducing agent according to claim 1 is characterized in that the concrete steps of this method are following:
The composition and the mass percent of the raw material that a. adopts are:
The big monomer 32 ~ 39% of unsaturated polyoxy Vinyl Ether
Vinylformic acid 2.4 ~ 3.3%
Acrylic ester monomer 0.8 ~ 1.6%
Cross-linking monomer 0 ~ 0.5%
Chain-transfer agent 0.08 ~ 0.19%
Initiator 0.16 ~ 0.33%
The deionized water surplus;
B. with above-mentioned raw materials under 80～90 ℃ of temperature, the reaction times is 1～4 hour, is cooled to 35 ℃～40 ℃ then, regulator solution pH value obtains water white solution to neutral, is the slowly-releasing collapse protective poly-carboxylic acid water reducing agent.
3. according to the preparation method of claims 1 described slowly-releasing collapse protective poly-carboxylic acid water reducing agent; It is characterized in that; The big monomer of described unsaturated polyoxy Vinyl Ether is allyl polyglycol ether or methacrylic polyglycol ether, and molecular weight is between 1000～2400.
4. according to the preparation method of claims 1 described slowly-releasing collapse protective poly-carboxylic acid water reducing agent, it is characterized in that described acrylic ester monomer is at least a in methyl acrylate, TEB 3K, ethyl propenoate, Hydroxyethyl acrylate, the Propylene glycol monoacrylate.
5. according to the preparation method of claims 1 described slowly-releasing collapse protective poly-carboxylic acid water reducing agent, it is characterized in that described cross-linking monomer is at least a in glycol methacrylate, triethylene Glycol double methyl methacrylate, the multicondensed ethylene glycol double methyl methacrylate.
6. according to the preparation method of claims 1 described slowly-releasing collapse protective poly-carboxylic acid water reducing agent, it is characterized in that described initiator is ammonium persulphate, Potassium Persulphate or Sodium Persulfate.
7. according to the preparation method of claims 1 described slowly-releasing collapse protective poly-carboxylic acid water reducing agent, it is characterized in that described chain-transfer agent is at least a in mercaptoethanol, Thiovanic acid, 2-Thiovanic acid, 3-Thiovanic acid, thiohydracrylic acid, methylpropene sodium sulfonate and the sodium allyl sulfonate.
8. according to the preparation method of claims 1 described slowly-releasing collapse protective poly-carboxylic acid water reducing agent, it is characterized in that described pH regulator agent is the aqueous solution of quadrol, trolamine, Pottasium Hydroxide or sodium hydroxide.
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